Quick drying polymeric coating

ABSTRACT

Improved agriculturally useful products are provided, including solid materials such as nitrogenous fertilizers (e.g., urea), together with a polycarboxylated polymer selected from the group consisting of a salts of copolymers containing individual quantities of maleic and itaconic moieties. The polymer composition also includes from about 10-60% by weight of an organic drying agent such as a lower alcohol which enhances the quick drying properties thereof. The compositions may also include an amount of boron, and bimodal vinylic polymer made up of quantities of high and low molecular weight (MW) vinylic polymers such as PVA.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of identically titled application Ser.No. 13/176,787 filed Jul. 6, 2011, which is a continuation ofapplication Ser. No. 12/651,356 of the same title filed Dec. 31, 2009,which is a continuation-in-part of application Ser. No. 12/351,589 filedJan. 9, 2009, entitled QUICK DRYING POLYMERIC FERTILIZER ADDITIVE. Allof these prior applications are incorporated in their entirety byreference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is broadly concerned with improved agriculturallyuseful, quick drying coating compositions and methods wherein thecompositions include one or more polycarboxylated polymer salt and avolatile organic drying agent. More particularly, the invention isconcerned with such compositions and methods wherein a copolymercontaining respective quantities of maleic and itaconic moieties issupplemented with a volatile drying agent, which may be mixed with orcoated onto solids, such as solid nitrogenous fertilizer. In anotheraspect of the invention, improved drying times are provided by addingboron, especially in conjunction with vinylic polymer(s) having amajority of pendent functional groups thereof as alcohols, andoptionally containing both relatively low and high molecular weight (MW)polymer fractions, to the copolymer-organic drying agent compositions.

2. Description of the Prior Art

U.S. Pat. No. 6,515,090 describes a highly useful class of copolymerswhich have been employed to good effect in a number of agriculturalapplications. For example, the '090 patent discloses copolymers made upof varying percentages of maleic and itaconic moieties, and saltsthereof, which can be applied to solid fertilizers to achieve surprisingincreases in yields. In normal practice, an aqueous copolymer mixture isapplied by spraying or other means onto solid fertilizers to providefertilizer-polymer compositions.

Specialty Fertilizer Products, LLC of Leawood, Kans., commercializes aseries of copolymers under the '090 patent. One such polymer,Nutrisphere-N® for granular nitrogen fertilizers, is especially designedto be applied to a variety of solid or granular nitrogen fertilizers,such as urea, ammonium salts, MAP, or DAP. This product is anapproximately 40% by weight solids aqueous dispersion of a 1:1 partialcalcium salt copolymer of maleic and itaconic moieties having a pH offrom about 3.25-3.75.

However, it has been found that, depending principally upon the moisturecontent of the solid fertilizer, suboptimal field applicationprocedures, or adverse ambient conditions such as very high humidity orlow temperatures, problems with successful application of theabove-mentioned compositions can arise. Specifically, the compositionsare sprayed or otherwise deposited on the outer surfaces of solidfertilizers and the water is allowed to evaporate by mass transfer,leaving a solid polymer residue coating. However, if the compositiondrying time is excessive resulting in incomplete drying of thecompositions, the coated products can be difficult to handle and apply.Indeed, in certain cases, relatively wet solid fertilizers with appliedaqueous copolymer can create agglomerations within field applicationequipment making it difficult or even impossible to evenly spread thecompositions across fields.

Mixtures of certain polycarboxylated polymers and organic solvents areknown, see U.S. Pat. No. 5,868,964, e.g., polyacrylic acid polymer plusmethanol. However, owing to the type of polymer used, and/or theconcentration of organic solvent, the polymer and solvent areessentially incompatible, resulting in viscous precipitates unsuitablefor use in fertilizer compositions. Polycarboxylate polymer salts do notusually form stable solutions in the presence of significantconcentrations of organic solvents such as methanol.

There is accordingly a need in the art for improved agriculturalproducts such as solid fertilizers in contact with quick-dryingpolycarboxylated polymers, so as to alleviate polymer coating and dryingproblems, while at the same time not detracting from the yield benefitsobtained using such polymers.

SUMMARY OF THE INVENTION

The present invention overcomes the problems outlined above and providesimproved polymer-containing, quick drying compositions designed forapplication with or onto various solids such as fertilizers, methods offorming the quick drying compositions and polymer-supplemented solidproducts, and methods of fertilizing soil to enhance plant growth usingpolymer-coated fertilizer compositions.

In broad outline, the fertilizer compositions of the invention include aquantity of a solid, fertilizer and a polymer-containing composition incontact with the solid fertilizer. The polymer-containing composition asinitially formulated and contacted with fertilizer includes a salt of apolycarboxylated polymer, namely a salt of a copolymer containingindividual quantities of maleic and itaconic moieties, along with avolatile organic drying agent or solvent. Thereafter, the drying agentevaporates, along with a substantial part of any water present, so thatthe fertilizer composition as applied to a field normally does notcontain these components to any substantial degree, but rather is madeup of the fertilizer plus the residue copolymer salt. Surprisingly, ithas been found that the selected polymer salts can be mixed with veryhigh concentrations of organic drying agent to produce stable liquidpolymer-containing compositions free of the incompatibility problems ofthe prior art. The final fertilizer composition can be prepared byapplying such a polymer-containing composition directly onto the surfaceof solid fertilizer at levels which enhance the plant growth and yieldcharacteristics of the complete fertilizer compositions, while at thesame time causing the rapid vaporization of excess moisture from thefertilizer compositions. This assures that the fertilizer compositionscan be field-applied using normal spreaders or the like without thedifficulties encountered with prior fertilizer compositions.

The methods of use of the fertilizer compositions involve applying thecompositions onto soil adjacent planted seeds or growing plants atnormal nitrogen levels.

Further improved results are realized when the above-described polymericcoating compositions are supplemented by a minor amount of boron(usually in the form of boric acid). Still more advantageous is the useof boron in conjunction with a vinylic polymer, preferably polyvinylalcohol (PVA), having a majority of the pendant functional groupsthereof as alcohols. Still more preferably, the vinylic polymer additiveis in the form of a bimodal polymer having respective fractions of highMW and low MW vinylic polymer.

It has been found that the fertilizer compositions of the inventionprovide significant increases in crop yields, and that the presence oforganic drying agents and other ingredients do not impede or otherwisealter such yield enhancements.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is predicated upon the discovery that solidagriculturally useful products such as fertilizers can be improvedthrough the use of quick drying polymeric compositions added to orapplied onto the solid products. Such drying agents facilitate andenhance the vaporization of moisture from the products, allowing easyuse thereof.

Virtually any fertilizer may be treated with the polymeric compositionsof the invention in order to lessen the formation of dust and to enhancethe fertilizer efficiency thereof. In preferred forms, however,nitrogen-bearing or nitrogenous fertilizers are improved in accordancewith the invention. For example, urea, ammonium sulfate, ammoniumnitrate and mixtures thereof are prime candidates for use in theinvention, and can be in any solid form such as prills or granules. Thesingle most preferred solid fertilizer is granular urea.

As indicated above, the polycarboxylated polymers of the invention areselected from the group consisting of copolymers in acid form or aspartial salts containing respective quantities of maleic and itaconicmoieties. These polymers preferably exist as partial salts, and caninclude mixtures of different salts. Virtually any desired cationicspecies may be used in the formation of the polymeric salts fromstarting acid polymers, particularly the alkali metals, alkaline earthmetals, ammonia, and the alkylamines (e.g., C1-C6 alkylamines such astriethylamine). The polymer salts of the invention are preferably in theform of aqueous dispersions, but non-aqueous organic dispersions mayalso be used.

The basic copolymers are described in U.S. Pat. No. 6,515,090, fully andcompletely incorporated by reference herein. In general, the copolymersalts should desirably contain from about 10-90% maleic moieties (morepreferably from about 25-75%), and correspondingly from about 90-10%itaconic moieties (more preferably from about 75-25%). The copolymersmay also contain other moieties apart from maleic and itaconic moieties,such as vinyl moieties. However, such other moieties should be presentonly up to a level of about 7%, i.e., the copolymers should containabout 93% maleic and itaconic moieties. Preferably, the copolymersconsist essentially of maleic and itaconic moieties. One particularlypreferred copolymer salt of this class is the previously-describedNutrisphere-N® for solid nitrogen fertilizers. More generally, suchcopolymer salts are preferably formed by the addition of a basicmaterial (e.g., Ca, Mg, K, Na in the form of the oxides, hydroxides, orcarbonates thereof) to achieve a desired pH in aqueous mixture, normallyin the range of from about 1-4.

The volatile organic drying agent may be made up of one or more organiccompounds, and is preferably selected from the group consisting oforganic alcohols and ketones, and particularly the C1-C4 alkyl alcohols.For reasons of cost, ease of use and vapor pressure characteristics,methanol is the most preferred drying agent. More broadly, however, thedrying agent may be selected from the group consisting of one or moreorganic compounds having a vapor pressure of at least about 40 mmHg atStandard Temperature and Pressure (STP). This embraces many of thepreferred lower alcohols such as methanol (127 mmHg), ethanol (59 mmHg)and isopropanol (42.7 mmHg).

The selected drying agent and polymer salt are preferably mixed togetherto form a polymer-containing composition designed to be applied to solidproducts such as nitrogenous fertilizers. In such cases thepolymer-containing composition normally comprises the polymer saltdissolved, suspended, or dispersed in a liquid phase comprising waterand the drying agent. The drying agent is normally used at a level offrom about 5-60% by weight (more preferably about 30-50% by weight, andmost preferably about 35-45% by weight) of the completepolymer-containing composition. Use of higher levels of drying agentwith the simultaneous presence of high polymer solids concentration mayrequire partial or essentially complete water removal by evaporation orother known means from the starting copolymer salt aqueous material.Thus, a preferred polymer-containing composition may include from about20-70% by weight of copolymer salt (more preferably from about 30-60% byweight), from about 30-50% by weight drying agent (more preferably fromabout 35-45% by weight), and from about 10-50% by weight water (morepreferably from about 10-25% by weight). An example of such apolymer-containing composition would include about 40% by weightmaleic-itaconic copolymer salt, about 45% by weight methanol, and about15% by weight water, and would have a pH 1-4 and a flash point of 74° F.Generally, the polymeric compositions should have a flash point ofgreater than 73° F.

Additional benefits are realized when compositions as described aboveare supplemented with boron alone, and more preferably in combinationwith bimodal vinylic polymers containing both high and low MW fractions.As used herein, “vinylic polymer” refers to any polymer or copolymerwherein a plurality of the repeat groups therein are vinyl alcoholmoieties. Generally, the low molecular weight vinylic polymer is used ina greater quantity than the high molecular weight materials, typicallyat ratios of from about 1:2 to 1:20, more preferably from about 1:4 to1:12, of the high MW to low MW materials.

The paradigm vinylic polymer is PVA. A large variety of PVAs areavailable commercially, and are typically distinguished on the bases ofmolecular weight and hydrolysis level, both ranging from “low” to“high.” Low MW PVAs have a number averaged molecular weight Mn in therange of up to about 15,000 (e.g., from about 7,000-13,000) and a weightaveraged molecular weight Mw in the range of about 25,000 (e.g., fromabout 13,000-23,000). These materials also have hydrolysis values offrom about 98.0-98.8% by mole, and a viscosity of from about 3.5-4.5 cps(as 4% aqueous solutions at 20° C.). High MW PVAs have an Mn of about70,000-101,000 and an Mw of 145,000 and above (e.g., from about146,000-186,000), hydrolysis values of 99.3% by mole, and viscosities offrom about 62-72 cps (as 4% aqueous solutions at 20° C.).

Normally, PVA or other polymeric molecular weights in commercialproducts have a distribution of molecular weights within some range.This distribution may be relatively wide or quite narrow, depending onthe specifics of a given product. Hence, these materials of mixtures areoften described by means of various averaged molecular weights (numberor weight averaged), and this is useful in understanding the propertiesof the products since a very large percentage of all molecules in thesample and a large fraction of the weight of the sample will havemolecular weights close to the averages. It is also common to depictmolecular weight distributions in polymers by means of a diagram havingmolecular weight along a horizontal axis and the relative abundance ofmolecules along a vertical axis. In the case of most polymercompositions, such diagrams are generally hump-shaped, typically havinga single peak where the apex thereof represents the weight which is themost common molecular weight in the polymer composition; this is oftentermed the “peak molecular weight,” referring to the weight of thehighest fraction of polymer molecules, and not the highest molecularweight in the composition. However, a bimodal vinylic polymercomposition of the invention exhibits two humps or peaks in such amolecular weight diagram. If an average molecular weight measurement istaken of such a bimodal system, highly misleading results may occur,because there will be relatively few molecules near such an “average”value. Thus, a bimodal and single mode polymer composition may have thesame “average” molecular weights, yet having very different physicalproperties.

In the present invention, it was found that better results may beobtained using bimodal vinyl polymer compositions having high and low MWfractions, as compared with a normal composition of the same averagemolecular weight. Use of bimodal compositions gives the best features ofboth high and low molecular weight polymers.

The preferred bimodal PVA is made up of individual amounts of low andhigh MW PVA, with the low MW PVA being present at a level of from about0.5-10% by weight of the complete fertilizer coating composition,whereas the high MW PVA is present at a level of from about 0.1-4% byweight. The low MW PVA fraction is normally present in an amount greaterthan that of the high MW PVA fraction, with the previously-describedhigh MW/low MW ratios being applicable.

It is well known that PVAs are highly biodegradable, water-solublepolymers that possess a range of properties, both in pure form and insolution. Such properties can make it difficult to formulate mixtures incertain situations. Thus, it is known that PVAs are at best poorlysoluble in solutions that contain significant amounts of organicsolvents, and precipitate in their presence. This is especially true ofhigh or super-high hydrolysis level grades of PVA, which simply do notdissolve in solutions having significant organic solvent levels inaddition to water. It is also known that PVA reacts rapidly with boratesto form what is conventionally called “silly putty” or “slime,” whichare insoluble crosslinked plastic materials.

PVAs of high or super-high hydrolysis levels can be used to createcoatings that are smooth and non-hygroscopic. Unfortunately, such PVAspossess very high viscosities and tend to make formulations which gelupon standing. Thus, these materials are per se impractical forfertilizer coating uses. On the other hand, low hydrolysis level PVAsexhibit low viscosities, but exhibit relatively high hygroscopicproperties.

Unexpectedly, it has been discovered that combinations of boron withselected PVAs avoid the formation of insolubles while also retainingmost of the water resistance of high MW PVA and the low viscosityproperties of low MW PVA. Particularly preferred in this context are thebimodal PVA compositions.

Preferred complete quick drying polymeric compositions in accordancewith the invention include: (1) from about 20-50% by weight of one ofmore of the previously described maleic-itaconic copolymers (morepreferably from about 35-45% by weight), advantageously in the form ofthe preferred partial calcium salt copolymer, with carboxylatesubstitution by calcium at levels of from about 1-35% (more preferablyfrom about 10-30%) of the carboxylates present, and a corresponding pHof from about 2.35-3.75 when the copolymer is in aqueous dispersion; (2)volatile organic solvent, preferably methanol, at a level of from about5-60% by weight (more preferably from about 35-50% by weight); (3) lowMW PVA at a level of from about 0.5-10% by weight (more preferably fromabout 2-6% by weight); (4) high MW PVA at a level of from about 0.1-4%by weight (more preferably from about 0.2-2% by weight); (5) a ratio ofhigh MW PVA to low MW PVA of from about 1:2 to 1:20 (more preferablyfrom about 1:4 to 1:12); (6) boric acid at a level of from about 0.5-5%by weight (more preferably from about 2-4% by weight); and (7) water asthe balance of the composition. Such a preferred coating compositiontypically has a solids level of from about 25-55% by weight, morepreferably from about 35-50% by weight.

Generally, the bimodal PVA is mixed with the maleic-itaconic copolymerwith heating to a level of from about 80-110° C. and agitation for aperiod of time to assure that the PVA fractions dissolve. The organicdrying agent is then added with additional stirring, followed by boricacid addition. In preferred preparative procedures, an aqueousmaleic-itaconic copolymer mixture at about 35% w/w solids content isplaced in a reactor at room temperature and stirred vigorously. The lowand high MW PVAs are then added, and the mixture is heated to 97° C.with continued vigorous stirring. This mixture is allowed to cook for 45minutes at 97° C. to insure that all of the PVA materials dissolve.Vacuum distillation of the mixture is then initiated until it reaches adesired solids concentration of approximately 60-70% w/w, whereupon themixture is allowed to cool to room temperature. Methanol is then addedwith vigorous stirring until the mixture becomes homogeneous. Finally,boric acid is added with further stirring until fully dissolved. Thecomplete polymeric composition contains approximately 40% solids w/w.

The polymeric compositions made up of an aqueous copolymer salt anddrying agent, with or without bimodal vinylic polymer and boron, can beapplied to agriculturally useful solid products such as solidfertilizers by any convenient means, such as by spraying or dipping. Thepreferred polymeric compositions were found to be unexpectedly andsurprisingly compatible and do not separate or precipitate solids. Ingeneral, the polymer-containing compositions are applied at a level offrom about 0.1-1 gallons of polymer-containing composition per ton offertilizer or other solid product (more preferably at a level of fromabout 0.3-0.8 gallons).

Although in preferred forms the ingredients of the coating compositionsare mixed together to form complete products before application to solidfertilizer, it would be possible to separately apply the copolymer salt,drying agent, and other ingredients, especially if done substantiallysimultaneously or in quick succession. In such cases, the rate ofapplication would be the same as that set forth above, considering themakeup of the two different applied substances. Moreover, the polymercompositions of the invention can be used on a variety of agriculturallyuseful products, such as seeds or soil amendments.

The quick drying compositions hereof may also be formulated includingvarious dyes, pigments, colorants, tracing agents, etc. Such practicesare well known in the agricultural arts. It is known that many dyes havepoor compatibility with entirely aqueous formulations of high ionicstrength. However, it was found that the present compositions containingappreciable volatile organic components can more readily be supplementedwith such dyes, and the effectiveness thereof in imparting color tosolid fertilizers is enhanced by the presence of the preferred PVA.

The following Examples set forth preferred polymer-containing quickdrying compositions of the invention and uses thereof. It is to beunderstood, however, that this example is provided by way ofillustration and nothing therein should be taken as a limitation uponthe overall scope of the invention.

Example 1

A fertilizer composition was prepared by applying a liquidpolymer-containing composition onto granular urea at a rate of ½ gallonof the liquid polymer-containing composition per ton of urea(urea+aqueous-methanol Nutrisphere-N®). The polymer-containingcomposition was made up of the above-described Nutrisphere-N® copolymersalt.

Another fertilizer composition was prepared using the aqueousNutrisphere-N® product applied at the same rate as above onto granularurea, but without the methanol drying agent (urea+aqueousNutrisphere-N®).

A final test fertilizer was straight uncoated urea (uncoated urea).

These three fertilizer compositions were field-tested to determine theeffect of the methanol drying agent on yields. This test was conductedin Courtland, Kans. in Crete silt loam soil, pH 6.5, organic matter2.2%, Bray P-one ranging from 19 ppm, soil test potassium 380 ppmammonium acetate extractable K. A no-till irrigated corn was planted(May 2) at 32,000 plants/acre on 6 test plots. The planted corn receiveda fluid fertilizer starter (10-34-0) at a rate of 8 gal. per acre,banded 2×2 beside each row. Sprinkler irrigation water was provided fromthe Lovewell Reservoir in north central Kansas.

The respective solid fertilizer compositions were applied at two rates,160 and 240 lb. Nitrogen per acre, as a broadcast applicationimmediately after corn planting. The 6 test plots were: uncoatedurea/160 lb. N/A; urea+aqueous Nutrisphere-N/160 lb. N/A;urea+aqueous-methanol Nutrisphere-N/160 lb. N/A; uncoated urea/240 lb.N/A; urea+aqueous Nutrisphere-N/240 lb. N/A; and urea+aqueous-methanolNutrisphere-N/240 lb. N/A. There was no incorporation of N into the soilexcept that which occurred via sprinkler irrigation.

The test plots were harvested November 2 by a plot combine taking thetwo center rows of each plot. Yield data was reported at 15.5% moisture.

Corn yield responses to the respective solid fertilizers were consistentand highly significant statistically (95% confidence interval). Themagnitude of improvement in yield of no-till corn receivingurea+aqueous-methanol Nutrisphere-N versus uncoated urea was similar tothat of urea+aqueous Nutrisphere-N polymer (Table 1).

These data indicate that the coating of urea with a high charge densitycopolymer salt has significant effects upon N use by corn withsubsequent increases in corn yield and potential profitability for thegrower. These data further confirm that the presence of the drying agenthas no deleterious effects upon the performance of the polymer-coatedurea.

TABLE 1 Enhancing N Availability for Irrigated Corn Treatments GrainYield lb N/A Form of N bu/A 160 Uncoated urea  173 b* 160 Urea +Nutrisphere-N ® 193 a 160 Urea + Experimental formulation 196 a 240Uncoated urea 180 b 240 Urea + Nutrisphere-N ® 196 a 240 Urea +Experimental formulation 197 a LSD_(.05) 11    CV % 3.8 *Means separatedby Duncan's multiple range test

Example 2

In this Example, a series of drying tests were conducted using variouscompositions including Nutrisphere-N® for granular nitrogen fertilizers(referred to as “Polymer” in Table 2 below), described above.

The formulations included various amounts of methanol and certain hadminor amounts of boric acid therein. Additionally, low and highmolecular weight PVA was added to certain of the formulations. The lowmolecular weight PVA (Celvol 103 sold by Celanese Chemical) had avariable molecular weight, a hydrolysis 98.4±0.4% by mole, and aviscosity of 4.0±0.5 cps (4% solution). The high molecular weight PVA(Celvol 165 sold by Celanese Chemical) had a variable molecular weight,a hydrolysis of 98.4±0.4% by mole, and a viscosity of 67±5.0 cps (4%solution).

In each test, one drop of the corresponding polymeric formulation wasplaced on a petrie dish, followed by stirring with the tip of a pipetteuntil the formulation was completely dry. The formulations and dryingtimes are set forth in Table 2.

TABLE 2 Formulation Polymer Methanol Boric Acid Low MW PVA High MW PVAWater Total Solids Drying Time No. % w/w % w/w % w/w % w/w % w/w % w/w %w/w (min) 1 40.8 0.0 0.0 0.0 0.0 59.2 40.8 4.1 2 40.0 44.0 0.0 0.0 0.016.0 40.0 3.0 3 39.0 43.0 3.0 0.0 0.0 15.0 42.0 2.4 4 35.0 35.0 0.0 4.50.5 25.0 40.0 4.5 5 36.2 38.1 2.9 3.3 0.5 19.0 42.9 1.0

The above data demonstrates that improved drying times were realized informulations

2, 3, and 5, as compared with the basic Nutrisphere-N® of Formulation 1.Surprisingly, the addition of boric acid (Formulation 3) alsosignificantly decreased drying times as compared with Formulation 2. Thebest drying times were obtained through the use of Formulation 5,including the use of bimodal PVA. This was an unexpected result, becauseFormulation 5 contains significantly more water than Formulations 2 and3, with a similar solids content. It is theorized that a synergisticeffect is obtained through the formation of a polymer-boron-PVA adduct,which exhibits very short drying times.

Inasmuch as conventional granular nitrogen fertilizer products aretypically coated to render them hard and resistant to moisture sorption,the petrie dish results of this test are predictive in a relative senseof the drying times of the formulations when applied to solid nitrogenfertilizers.

1. A method of forming a fertilizer composite for application to soil,comprising the steps of: initially applying a polymer-containingcomposition onto a quantity of solid fertilizer, said polymer-containingcomposition including a substantially water soluble copolymer containingindividual quantities of maleic and itaconic moieties, water, and anorganic compound drying agent; and thereafter allowing said drying agentand a substantial part of the water present in the composite toevaporate from said fertilizer to leave the dried residue of saidpolymer-containing composition on the fertilizer, so that the compositedoes not include said drying agent or water to any substantial degree,whereby said composite as applied to soil does not have any substantialpresence of the drying agent and water which formed a part of thepolymer-containing composition initially applied to said solid product.2. The method of claim 1, said copolymer containing from about 10-90%maleic moieties, and from about 90-10% itaconic moieties.
 3. The methodof claim 2, said copolymer consisting essentially of said maleic anditaconic moieties.
 4. The method of claim 1, said drying agent selectedfrom the group consisting of organic alcohols and ketones.
 5. The methodof claim 4, said drying agent selected from the group consisting ofC1-C4 alcohols.
 6. The method of claim 1, said organic drying agentbeing present at a level of from about 5-60% by weight in saidpolymer-containing composition.
 7. The method of claim 1, said copolymerbeing in partial salt form and having at least about 93% itaconic andmaleic moieties.
 8. The method of claim 1, said polymer-containingcomposition comprising from about 20-70% by weight of said copolymer inpartial salt form, from about 5-60% by weight methanol, and from about10-50% by weight water.
 9. The method of claim 8, said copolymer saltbeing present at a level of from about 30-60% by weight, from about30-50% by weight methanol, and from about 10-25% by weight water. 10.The method of claim 1, said polymer-containing composition includingfrom about 0.5-5% by weight boron as boric acid.
 11. The method of claim10, said polymer-containing composition including an amount of bimodalvinyl polymer therein, said bimodal vinyl polymer including individualhigh and low molecular weight vinyl polymer fractions.
 12. The method ofclaim 10, said vinyl polymer being polyvinyl alcohol (PVA), the ratio ofsaid high MW PVA to said low MW PVA being from about 1:2 to 1:20. 13.The method of claim 12, said ratio being from about 1:4 to 1:12.
 14. Themethod of claim 1, said fertilizer selected from the group consisting ofurea, ammonium sulfate, ammonium nitrate, and mixtures thereof in theform of granules or prills.
 15. The method of claim 1, saidpolymer-containing composition applied to the surface of said fertilizerat a level of from about 0.1-1 gallons of said polymer-containingcomposition per ton of said solid fertilizer.